JP2017034454A - Electronic component and manufacturing method of electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress a secular change of a frequency in an electronic component encapsulating a crystal oscillator in which an excitation electrode containing silver as a main material is provided in a crystal piece via a contact layer and of which the frequency is adjusted by shaving the excitation electrode, in a container in an airtight manner.SOLUTION: A crystal oscillator is configured by laminating a contact layer 4, a base layer consisting of Bi and a main electrode layer 300 on a crystal piece 10 in this order. When fixing the crystal oscillator to a container, a conductive adhesive is heated and hardened, and Bi in the base layer is dispersed within the main electrode layer 300. By then shaving surfaces of excitation electrodes 31 and 32, frequency adjustment is performed, the container is heated and sealed thereafter, and a nearby layer enriched in Bi is segregated on a surface of the main electrode layer 300. Therefore, a state where a layer 51 of Bi is formed on the surfaces of the excitation electrodes 31 and 32 is obtained after the frequency adjustment.SELECTED DRAWING: Figure 9

Description

  The present invention relates to an electronic component in which a piezoelectric vibrator having a silver electrode is hermetically sealed in a container.

  Piezoelectric resonators, such as AT-cut crystal resonators mounted on ceramic packages, are widely used as various frequency control devices, including mobile communication terminals, because they are small, highly accurate, and highly stable. Has been. A surface-mount crystal unit (SMD crystal unit) has a structure in which a crystal unit is hermetically sealed in a ceramic package as follows. That is, the quartz resonator is formed with an excitation electrode and an extraction electrode extending from the excitation electrode toward the end of the quartz piece at opposite positions of both main surfaces of the quartz piece cut into a strip shape. The lead electrode of the child and the routing wiring terminal in the ceramic package (base) are conductively fixed using a conductive adhesive or the like, and the ceramic package (base) and the ceramic or metal lid are connected to the low melting glass or metal sealing material. Is hermetically sealed. Depending on the type of low-melting glass or metal sealing material used for sealing, in the hermetic sealing process, the crystal resonator and the resonator package are placed at a high temperature of 300 to 400 ° C.

As the electrode material, gold (Au) or silver (Ag) formed by vapor deposition or sputtering is used. Although the crystal resonator of the Au electrode has high long-term frequency stability, there is a problem that the material cost is high. On the other hand, the crystal resonator of the Ag electrode has a problem that it is inferior in long-term frequency stability (aging characteristic) although it is cheaper than the Au electrode.
It is considered that the change with time in the frequency of the pure Ag electrode crystal resonator is caused by Ag aggregation due to heat in the hermetic sealing process. That is, the mass change of the excitation electrode due to gas adsorption or oxidation from the package inner wall, adhesive, or sealing atmosphere is known, but the surface area of the Ag electrode increases due to aggregation, and the amount of gas adsorption and surface oxidation increases. This is presumed to be the cause of frequency fluctuations.

  In order to suppress aggregation in a pure Ag thin film, it is known that addition of trace metals is effective. For example, in Patent Document 1, bismuth (Bi) and / or antimony (Sb) are contained in a total amount of 0.005 to 0.40% (atomic%:% of the number of atoms when the number of constituent atoms is 100%). An Ag-based alloy is disclosed. On the other hand, Patent Document 2 discloses an Ag—In alloy having a component composition containing 0.1 to 1.8 atomic% of indium (In), the balance being Ag and inevitable impurities. Both are patents aimed at suppressing light reflectance deterioration due to Ag aggregation, but the added metal (Bi, Sb or In) is deposited as a segregation layer on the surface of the thin film, and the surface segregation layer is in the atmosphere. When a stable oxide film is formed by exposure to oxygen therein, agglomeration is suppressed and reflectance deterioration can be prevented.

  When the Ag-based alloys of Patent Documents 1 and 2 are used for the electrodes of a crystal resonator, there are the following problems. That is, when manufacturing a crystal resonator, there is a step of adjusting the resonance frequency of the resonator by scraping the electrode film with an ion beam or a laser. When used as an electrode, the surface segregation layer formed as aggregation suppression is scraped off during frequency adjustment, the effect of aggregation suppression is greatly reduced, and frequency fluctuations due to changes over time are not reduced.

JP 2004-139712 A JP 2014-19922

  The present invention has been made under such circumstances, and an object of the present invention is to provide an excitation electrode in which an adhesion layer and a main electrode layer made of silver are laminated in this order on a piezoelectric piece. An object of the present invention is to provide a technique for suppressing a change in frequency over time in an electronic component in which a piezoelectric vibrator whose frequency is adjusted by cutting an electrode is hermetically sealed in a container.

The electronic component of the present invention is provided with an excitation electrode in which an adhesion layer and a main electrode layer mainly composed of silver are laminated in this order on a piezoelectric piece, and the frequency is adjusted by cutting the excitation electrode. In an electronic component configured by hermetically sealing a vibrator in a container,
Preliminarily provided between the main electrode layer and the adhesion layer, and at least part of the base layer made of a metal that forms a eutectic with respect to silver is diffused into the main electrode layer, and after the frequency adjustment, The surface of the metal is segregated on the surface.

  In the electronic component of the present invention, the metal that forms a eutectic with respect to silver may be a metal selected from yttrium, cerium, copper, silicon, germanium, lead, and bismuth.

The method of manufacturing an electronic component of the present invention is a method of manufacturing an electronic component configured by hermetically sealing a piezoelectric vibrator in which an excitation electrode mainly composed of silver is provided on a piezoelectric piece in a container.
A laminating step of laminating an adhesion layer on the piezoelectric piece, a base layer made of a metal that forms a eutectic with silver, and a main electrode layer mainly composed of silver in this order;
Thereafter, the surface of the main electrode layer is shaved to adjust the frequency of the piezoelectric vibrator,
Next, the piezoelectric vibrator is heated to obtain an excitation electrode in which the metal is segregated on the surface of the main electrode layer.

In the electronic component manufacturing method of the present invention, the piezoelectric vibrator is fixed to the container with the conductive adhesive before the step of adjusting the frequency of the piezoelectric vibrator after the laminating step, and the conductive adhesive is heated. And curing it,
Due to the heating of the conductive adhesive, at least a part of the base layer diffuses into the main electrode layer, and the metal diffused into the main electrode layer is heated by the piezoelectric vibrator after the frequency adjustment. It may be segregated on the surface, and the step of heating the piezoelectric vibrator after the frequency adjustment may be a step of heating to hermetically seal the container.

  The present invention relates to an electronic component configured by hermetically sealing a piezoelectric vibrator in a container, and an adhesive layer, a base layer made of a metal eutectic with silver and a main electrode layer made of silver in this order on the piezoelectric piece. After laminating and adjusting the frequency by scraping the surface of the main electrode layer, the main electrode layer is heated, and the metal is segregated on the surface of the excitation electrode to constitute the excitation electrode. Therefore, the unevenness of the surface of the excitation electrode is reduced, and gas adsorption and oxidation are suppressed. Therefore, it is possible to suppress a change in the frequency of the piezoelectric vibrator over time.

It is a disassembled perspective view which shows the electronic component which concerns on embodiment of this invention. 1 is a plan view showing a crystal resonator according to an embodiment of the present invention. 1 is a cross-sectional view showing a crystal resonator according to an embodiment of the present invention. It is sectional drawing to which the laminated body was expanded. It is a phase diagram which shows the relationship between Ag and Bi. It is explanatory drawing which shows the main electrode layer after the film-forming process. It is explanatory drawing which shows the main electrode layer after the heating of a conductive adhesive. It is explanatory drawing which shows the main electrode layer after the etching of the electrode surface. It is explanatory drawing which shows the main electrode layer after the airtight sealing of a container. FIG. 6 is a characteristic diagram showing an Auger electron depth direction analysis spectrum according to Sample 1. FIG. 6 is a characteristic diagram showing an Auger electron depth direction analysis spectrum according to Sample 2. FIG. 6 is a characteristic diagram showing an Auger electron depth direction analysis spectrum according to Sample 3. FIG. 6 is a characteristic diagram showing a change with time in the frequency of a crystal resonator according to Example 2. 6 is a characteristic diagram showing a change with time of a frequency of a crystal resonator according to Comparative Example 2.

  A vibrator package which is an electronic component according to an embodiment of the present invention will be described. As shown in FIG. 1, the vibrator package includes a container 2 and a crystal vibrator 1. The container 2 includes a ceramic base body 20 that is open at the top and is formed in a substantially box shape, and a ceramic lid body 21 that closes the opening of the base body 20. On the inner bottom surface of the base body 20, an electrode 22 electrically connected to an electrode pad (not shown) provided on the bottom bottom surface side of the base body 20 is formed.

  As shown in FIGS. 2 and 3, the crystal resonator 1 has excitation electrodes 31 and 32 opposed to a main surface on one surface side and a main surface on the other surface side of an AT-cut crystal piece 10 cut into a strip shape. It is provided as follows. One end of the extraction electrode 33 is connected to a part of the excitation electrode 31 on one side so as to be extracted toward the peripheral edge on one side of the crystal piece 10, and the other end of the extraction electrode 33 is connected to the crystal piece 10. An electrode end 35 is formed by being routed around one side edge on the other surface side of the crystal piece 10 through one side surface. Further, one end of the extraction electrode 34 is connected to a part of the excitation electrode 32 on the other surface side so as to be extracted toward the peripheral edge on one side, and the other end side of the extraction electrode 34 is on the other surface side of the crystal piece 10. An electrode end 36 is formed by being drawn around one side periphery.

  The excitation electrodes 31 and 32 will be described along a method for manufacturing a vibrator package. The extraction electrodes 33 and 34 and the electrode ends 35 and 36 are also formed by the same process as that of the excitation electrodes 31 and 32, and the excitation electrodes 31 and 32 will be described as an example. As shown in FIG. 4, an adhesion layer 4 made of chromium (Cr), a base layer 5 made of Bi, and a main electrode layer 30 made of Ag or an Ag-based alloy mainly composed of Ag are formed on the front and back surfaces of the crystal piece 10. A stacked body that is sequentially stacked is provided. The film thickness of the adhesion layer 4 is not particularly limited, but sufficient adhesion can be obtained if it is in the range of 0.5 to 10 nm. The thickness of the underlayer 5 is not particularly limited, but may be in the range of 0.5 to 50 nm. The film thickness of the main electrode layer 30 made of Ag or an Ag-based alloy containing Ag as a main component affects the characteristics of the crystal resonator 1 and is determined by the resonator characteristics such as the size and the resonance frequency of the crystal resonator 1. Is done. Typically, it is 100 to several hundred nm. The adhesion layer 4, the base layer 5, and the main electrode layer 30 made of Ag or an Ag-based alloy containing Ag as a main component are formed by resistance heating type vapor deposition, electron beam vapor deposition, sputtering, or the like. The adhesion layer 4 may be, for example, titanium (Ti), nickel (Ni), nickel tungsten (NiW), aluminum (Al), or the like. At this time, since the Ag layer constituting the main electrode layer 30 and the Bi layer constituting the underlayer 5 are in contact with each other, the Bi atom 50 is Ag or Ag containing Ag as a main component as shown in FIG. It diffuses through the grain boundaries of the base alloy layer.

  Subsequently, as shown in FIG. 1, the electrode 22 on the base body 20 side and the electrode ends 35 and 36 of the crystal resonator 1 are electrically connected by the conductive adhesive 6. Thereafter, for example, the conductive adhesive 6 is cured by heating at 200 ° C. for 30 minutes, and the crystal unit 1 is fixed to the base body 20 (heating step for curing the conductive adhesive 6).

  Here, Ag, which is the main component of the main electrode layer 30, and Bi, which is the main component of the underlayer 5, have a phase diagram that becomes a eutectic as shown in FIG. , Ag, and Bi are both present in a substantially solid state. Therefore, Bi atoms 50 diffused in the main electrode layer 30 are difficult to diffuse into the crystal grains of Ag or an Ag-based alloy layer containing Ag as a main component, and Ag and Bi have a property of being easily separated. Accordingly, in the heating step of curing the conductive adhesive 6, when the crystal unit 1 is heated, as shown in FIG. 7, the diffusion of the underlayer 5 further proceeds into the main electrode layer 30, and a part of the main electrode In addition to segregation on the surface of the layer 30, Bi is rich in a layer deeper than the layer on which Bi is segregated. Further, almost all of the underlayer 5 diffuses into the main electrode layer 30 and disappears. Thereafter, the surface of the main electrode layer 30 is shaved by an ion beam or a laser, and the resonance frequency of the crystal unit 1 is adjusted. The surface of the main electrode layer 30 on the other surface side of the crystal piece 10 is scraped by a laser or the like transmitted through the crystal piece 10. At this time, as shown in FIG. 8, in the main electrode layer 30, a part of Bi atoms 50 segregated on the surface layer side is also removed.

  Subsequently, as shown in FIG. 1, an adhesive 23 such as a low-melting glass or a metal sealing material is applied to the periphery on the lower surface side of the lid body 21, and the lid body 21 is placed on the upper surface of the peripheral wall of the base body 20 in a nitrogen gas atmosphere. For example, heat treatment at 360 ° C. for 30 minutes to hermetically seal the container 2 (heating process for hermetically sealing the container 2). By the heat treatment at this time, in the main electrode layer 30, the Bi rich layer formed deeper than the layer on which the surface Bi is segregated before the frequency adjustment is further segregated. As a result, as shown in FIG. 9, the main electrode layer 300 in which the adhesion layer 4 and the Bi layer 51 are formed on the crystal piece 10 is formed in this order, and the excitation electrodes 31 and 32 are formed. .

  Ag has low adhesion to quartz, and the main electrode layer 30 is easily peeled off when the main electrode layer 30 made of Ag or an Ag-based alloy containing Ag as a main component is provided directly on the crystal piece 10. Therefore, by providing the adhesion layer 4, when the underlayer 5 diffuses into the main electrode layer 30 and gradually becomes a thin layer, or when all of the underlayer 5 diffuses into the main electrode layer 30, the main electrode layer Since 30 is formed on the crystal piece 10 via the adhesion layer 4, peeling of the main electrode layer 30 can be suppressed.

As described in the background art, Ag has a property of being aggregated by heating. Therefore, when heating is performed to hermetically seal the container 2, the surface irregularities of the excitation electrodes 31 and 32 become larger due to Ag aggregation, and the surface area becomes larger. As a result, the gas is easily adsorbed on the surfaces of the excitation electrodes 31 and 32, the amount of surface oxidation increases, and the frequency of the crystal unit 1 is likely to change.
On the other hand, since Bi has the property of being easily oxidized, the outermost surface of the Bi layer 51 segregated on the surfaces of the excitation electrodes 31 and 32 is covered with Bi oxide. Due to the presence of the surface oxide film, the excitation electrodes 31 and 32 having the Bi layer 51 formed on the surface thereof have less surface irregularities when heated in order to hermetically seal the container 2, and the surface area is reduced. Get smaller. Therefore, the adsorption of gas on the surfaces of the excitation electrodes 31 and 32 is suppressed, the amount of oxidation on the surface is reduced, and the change with time of the frequency of the crystal unit 1 is suppressed.

  In the embodiment described above, in the resonator package configured by sealing the crystal resonator 1 in the container 2, the adhesion layer 4, the base layer 5 made of Bi, and the main electrode layer 30 are formed on the crystal piece 10. In order to fix the crystal resonator 1 to the container 2, the conductive adhesive 6 is heated and cured to diffuse Bi in the underlayer 5 into the main electrode layer 30. . Then, after adjusting the frequency by scraping the surface of the main electrode layer 30, the container 2 is heat-sealed, and Bi is segregated on the surface of the main electrode layer 30. Therefore, the excitation electrodes 31 and 32 in which the Bi layer 51 is formed on the surface of the main electrode layer 30 after the frequency adjustment are obtained. Therefore, the unevenness of the surfaces of the excitation electrodes 31 and 32 is reduced, and gas adsorption and oxidation are suppressed, so that a change with time in the frequency of the crystal unit 1 can be suppressed.

  Further, in the above-described embodiment, it has been described that almost all Bi as the base layer 5 diffuses into the main electrode layer 30, but a part of Bi is not diffused and remains in the lower layer of the main electrode layer 300. Even if it is, the same effect can be acquired.

The metal used for the underlayer 5 may be any metal that forms a eutectic with respect to Ag used as the main electrode layer 30, but the metal used as the main electrode layer 30, the metal used as the underlayer 5, Are more preferably independent from each other because the eutectic is stably formed. Therefore, when Ag is used as the main material of the excitation electrodes 31 and 32, as the underlayer 5, Y (yttrium), cerium (Ce), copper (Cu), silicon (Si), germanium (Ge), lead (Pb) Etc. can be used.
The piezoelectric piece is not limited to the AT-cut crystal piece 10, and may be a crystal piece having a different cut such as a DT cut, or a piezoelectric body made of lithium tantalate, lithium niobate, or the like.

[Example 1]
Excitation electrodes 31 and 32 were formed on the quartz resonator 1 and the composition ratio of atoms in the depth direction of the excitation electrode 31 on one side was examined. A main electrode layer 30 composed of 2 nm of Cr serving as the adhesion layer 4, 10 nm of Bi serving as the underlayer 5, and Ag of 250 nm was formed on the AT-cut crystal piece 10 in the order of 250 nm by sputtering. Thereafter, heating was performed at 200 ° C. for 30 minutes in the same manner as the step of heating and curing the conductive adhesive 6 described in the embodiment, and then the surfaces of the excitation electrodes 31 and 32 were irradiated with an ion beam to etch the surface. . Further, after that, the container 2 was heated at 360 ° C. for 30 minutes in the same manner as the heating process for hermetic sealing of the container 2 shown in the embodiment. The laminate immediately after laminating the adhesion layer 4, the underlayer 5, and the main electrode layer 30 is sample 1, and immediately after heating at 200 ° C. for 30 minutes, the excitation electrodes 31 and 32 before etching the surface of the laminate. Sample 3 was a laminate after heating at 360 ° C. for 30 minutes. Sample 3 corresponds to excitation electrodes 31 and 32 obtained in the embodiment of the present invention.

  Auger electron analysis in the depth direction of each of samples 1 to 3 was performed, and the ratio of each atom of Ag, Bi, O (oxygen), and Si was examined. 10 to 12 show the results, and are characteristic diagrams showing the composition ratios of Ag, Bi, O, and Si atoms with respect to the etching time (depth from the surface of the excitation electrodes 31 and 32) in Samples 1 to 3, respectively. It is. Although Si appears to diffuse in the excitation electrodes 31 and 32, the background level of Si in Auger electron analysis is about 10 atomic% in composition. Therefore, the Si ratio being 10 atomic% or less indicates that Si is not diffused in the excitation electrodes 31 and 32. That is, it can be said that the Si of the crystal piece 10 is not diffused into the excitation electrodes 31 and 32.

  As shown in FIG. 10, the base layer 5 has already started to diffuse into the main electrode layer 30 immediately after the sample 1 is formed. As shown in FIG. 11, before the frequency adjustment of the sample 2, the diffusion of the Bi atoms 50 further proceeds, and partly segregates on the electrode surface of the main electrode layer 30, and Bi is deeper than the surface segregation layer. A rich state has been realized. Further, almost all of the underlayer 5 formed on the adhesion layer 4 is diffused into the main electrode layer 30 and disappears. Then, in the state after the hermetic sealing of the sample 3 shown in FIG. 12, the Bi-rich layer under the surface segregation layer before the frequency adjustment disappears, and segregates on the surface of the main electrode layer 30 after the frequency adjustment. ing. When the frequency is adjusted, the surface segregation layer in Sample 2 and a part of the layer rich in Bi are removed by etching, but the remaining part of the layer rich in Bi is heated at 360 ° C. for 30 minutes to obtain the main electrode. It is considered that segregated on the surface of the layer 30.

[Example 2]
On the AT-cut crystal piece 10, as Example 2, a 2 nm-thick adhesion layer 4 made of Cr, a 10 nm-thick base layer 5 made of Bi, and a 250-nm-thick main electrode layer made of Ag 30 MHz crystal resonators laminated in this order from the lower layer side, and as a comparative example 2, a 2 nm thick adhesion layer composed of Cr, and a main electrode layer composed only of Ag, A 27 MHz crystal resonator laminated in order was formed. The crystal resonators of Example 2 and Comparative Example 2 were mounted on a ceramic container with a silicone-based conductive adhesive, heated at 200 ° C. for 30 minutes to cure the conductive adhesive, and the crystal resonator was fixed. Thereafter, the surface of the excitation electrode is etched with an ion beam to adjust the frequency, and then the container is hermetically sealed by heat treatment at 360 ° C. for 30 minutes using a low-melting glass in a nitrogen atmosphere. did.

  Thereafter, 10 vibrator packages according to Example 2 and 10 vibrator packages according to Comparative Example 2 were stored under a temperature condition of 85 ° C., and the vibrator package according to Example 2 was stored for 1 day, 2 days. The oscillation frequency Fa was measured after the elapse of 4, 8, 11, 21, and 31 days. For the resonator package according to Comparative Example 2, the oscillation frequency Fa was measured after the elapse of 1 day, 2 days, 5 days, 8 days, 11 days, 21 days, 31 days, and 41 days. In each of Example 2 and Comparative Example 2, a frequency difference ΔF (= Fa−F) with respect to the frequency F on the 0th day was obtained, and a frequency fluctuation amount (ΔF / F) was obtained. The frequency fluctuation of the crystal unit under high-temperature environment storage is a phenomenon called aging deterioration. Aging deterioration is a so-called thermal activation process in which the amount of frequency fluctuation increases as the storage temperature increases. The amount of frequency fluctuation after storage for 21 days corresponds to the amount of frequency fluctuation when one year has passed at room temperature (25 ° C.). With respect to the time-dependent change in the frequency fluctuation amount of the crystal resonator in Example 2 and Comparative Example 2, for the sake of illustration, the time-dependent change in the frequency fluctuation amount is shown in FIG. ) And FIG. 14 (Comparative Example 2).

  In the crystal resonator of Example 2, the average frequency variation amount of the ten resonator packages is −2.3 ppm when 21 days have elapsed, and the variation in the frequency variation amount between the respective resonator packages is ± It was 0.7 ppm. On the other hand, in the crystal resonator of Comparative Example 2, the average frequency fluctuation amount of the ten vibrator packages is −3 ppm when 21 days have elapsed, and the variation in the frequency fluctuation amount between the vibrator packages is ± 2 0.0 ppm. Further, in Example 2, the frequency fluctuation amount and the variation in the frequency fluctuation amount have not changed after the 21st day, but in the comparative example 2, both the frequency fluctuation amount and the variation in the frequency fluctuation amount are large.

  According to this result, it can be seen that the crystal resonator in Example 2 has a smaller variation in the amount of frequency variation with time between each resonator package than the crystal resonator in Comparative Example 2. This is presumed that in Example 2, Bi was segregated on the surface of the excitation electrode, and this Bi layer suppressed gas adsorption and oxidation, and the change with time was small.

1 Crystal resonator 2 Container
4 Adhesive Layer 5 Underlayer 6 Conductive Adhesive 10 Crystal Piece 30 Main Electrode Layers 31, 32 Excitation Electrode 50 Bi Atom 51 Bi Layer

Claims (5)

An excitation electrode in which an adhesion layer and a main electrode layer mainly composed of silver are laminated in this order is provided on the piezoelectric piece, and the piezoelectric vibrator whose frequency is adjusted by cutting the excitation electrode is hermetically sealed in the container. In an electronic component configured by sealing,
Preliminarily provided between the main electrode layer and the adhesion layer, and at least part of the base layer made of a metal that forms a eutectic with respect to silver is diffused into the main electrode layer, and after the frequency adjustment, An electronic component characterized in that the metal is segregated on the surface.   2. The electronic component according to claim 1, wherein the metal forming a eutectic with respect to silver is a metal selected from yttrium, cerium, copper, silicon, germanium, lead and bismuth. In a method of manufacturing an electronic component configured by hermetically sealing a piezoelectric vibrator in which a piezoelectric electrode having an excitation electrode mainly composed of silver provided on a piezoelectric piece is sealed in a container,
A laminating step of laminating an adhesion layer on the piezoelectric piece, a base layer made of a metal that forms a eutectic with silver, and a main electrode layer mainly composed of silver in this order;
Thereafter, the surface of the main electrode layer is shaved to adjust the frequency of the piezoelectric vibrator,
And a step of heating the piezoelectric vibrator to obtain an excitation electrode in which the metal is segregated on the surface of the main electrode layer. After the laminating step, before the step of adjusting the frequency of the piezoelectric vibrator, including fixing the piezoelectric vibrator to the container with a conductive adhesive and heating and curing the conductive adhesive,
Due to the heating of the conductive adhesive, at least a part of the base layer diffuses into the main electrode layer, and the metal diffused into the main electrode layer is heated by the piezoelectric vibrator after the frequency adjustment. 4. The method of manufacturing an electronic component according to claim 3, wherein segregation occurs on the surface.   The method of manufacturing an electronic component according to claim 3 or 4, wherein the step of heating the piezoelectric vibrator after the frequency adjustment is a step of heating in order to hermetically seal the container.

Images